EP0244288B1 - Mesomorpher Polymerwirkstoff, verwendungsfähig zur Nichtlinearoptik - Google Patents

Mesomorpher Polymerwirkstoff, verwendungsfähig zur Nichtlinearoptik Download PDF

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Publication number
EP0244288B1
EP0244288B1 EP87400816A EP87400816A EP0244288B1 EP 0244288 B1 EP0244288 B1 EP 0244288B1 EP 87400816 A EP87400816 A EP 87400816A EP 87400816 A EP87400816 A EP 87400816A EP 0244288 B1 EP0244288 B1 EP 0244288B1
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grouping
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component
spacer
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EP0244288A1 (de
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Pierre Le Barny
Gilles Ravaux
Jean-Claude Dubois
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Thales SA
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Thomson CSF SA
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    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/35—Non-linear optics
    • G02F1/355—Non-linear optics characterised by the materials used
    • G02F1/361—Organic materials
    • G02F1/3615—Organic materials containing polymers
    • G02F1/3617—Organic materials containing polymers having the non-linear optical group in a side chain
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F8/00—Chemical modification by after-treatment
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K19/00—Liquid crystal materials
    • C09K19/04—Liquid crystal materials characterised by the chemical structure of the liquid crystal components, e.g. by a specific unit
    • C09K19/38—Polymers
    • C09K19/3833—Polymers with mesogenic groups in the side chain
    • C09K19/3842—Polyvinyl derivatives
    • C09K19/3852—Poly(meth)acrylate derivatives
    • G—PHYSICS
    • G02—OPTICS
    • G02F—OPTICAL DEVICES OR ARRANGEMENTS FOR THE CONTROL OF LIGHT BY MODIFICATION OF THE OPTICAL PROPERTIES OF THE MEDIA OF THE ELEMENTS INVOLVED THEREIN; NON-LINEAR OPTICS; FREQUENCY-CHANGING OF LIGHT; OPTICAL LOGIC ELEMENTS; OPTICAL ANALOGUE/DIGITAL CONVERTERS
    • G02F1/00—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics
    • G02F1/01—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour 
    • G02F1/061—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on electro-optical organic material
    • G02F1/065—Devices or arrangements for the control of the intensity, colour, phase, polarisation or direction of light arriving from an independent light source, e.g. switching, gating or modulating; Non-linear optics for the control of the intensity, phase, polarisation or colour  based on electro-optical organic material in an optical waveguide structure
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09K—MATERIALS FOR MISCELLANEOUS APPLICATIONS, NOT PROVIDED FOR ELSEWHERE
    • C09K2323/00—Functional layers of liquid crystal optical display excluding electroactive liquid crystal layer characterised by chemical composition
    • C09K2323/05—Bonding or intermediate layer characterised by chemical composition, e.g. sealant or spacer

Definitions

  • the present invention relates to polymeric materials. usable in nonlinear optics. More precisely, it relates to a new type of material which, suitably oriented, is capable of generating with high efficiency the second harmonic of an electromagnetic wave whose wavelength can be between 300 nm and 2000 nm.
  • the materials most commonly used to obtain the phenomenon of generation of second harmonic are mineral single crystals such as lithium niobiate or lithium dihydrogen phosphate.
  • Organic materials active in the generation of second harmonics have the particularity of exhibiting on the molecular scale a very large asymmetry of electronic density. This is the case for example with 4-N-dimethylamino-4'-nitrostilbene (DANS). But for the compound to give rise to the phenomenon of generation of second harmonic, it is also necessary that the molecular arrangement preserves on the macroscopic scale the asymmetry of electronic density which exists on the molecular scale. To satisfy this condition, it is necessary to obtain non-centrosymmetric single crystals. However, the success rate in obtaining such crystals is only 20% with the non-chiral compounds. Indeed, molecules like DANS have a strong permanent dipole moment and go head to tail, which leads to a centrosymmetric system.
  • DANS 4-N-dimethylamino-4'-nitrostilbene
  • the invention proposes to increase the efficiency of the material by fixing, by means of a covalent bond, the entity generating the second harmonic and the mesogenic group on the same polymer skeleton. This makes it possible to obtain materials with a high content of functions generating second harmonics.
  • the nematic copolymer used by Meredith, Van Dusen and Williams in the review cited above is shown in Figure 1.
  • the backbone of this copolymer is polymethacrylate.
  • this copolymer serving as matrix only 2% by weight of 4N dimethylamino 4 'nitrostilbene (DANS) can be dissolved by weight, the chemical formula of which is shown in FIG. 2.
  • DANS dimethylamino 4 'nitrostilbene
  • the polymeric material according to the invention has the structure shown in FIG. 3. It is formed from two monomers 1 and 2, the molar fractions of which are 1-x and x respectively.
  • the polymeric material is therefore formed of a skeleton 3, each of the monomers 1 and 2 having a constituent element of this skeleton, and of side chains.
  • the monomer 1 comprises a mesomorphogenic group 4 linked to the skeleton 3 by a spacer 5.
  • the monomer 2 comprises a group 6 having a high hyperpolarizability and able to generate the second harmonic of an electromagnetic wave. This group 6 is connected to the skeleton 3 by a spacer 7.
  • the copolymer according to the invention must have the following properties. It must be amorphous at room temperature and have a glass transition temperature above room temperature. It must have a single mesophase, preferably nematic since it is the one that is most easily oriented under the effect of an electric field. To meet these requirements, the constituent elements of the copolymer will be chosen as follows.
  • the backbone 3 of the copolymer may be a polymethacrylate, a polyacrylate, a polychloroacrylate or a polysiloxane. Spacers 5 and 7 will be of the type - (CH 2 ) n with 2 ⁇ ns 15 or - (CH 2 -CH 2 -O) - n with 1 ⁇ n to 5.
  • spacers 5 and 7 are not not necessarily identical for the same copolymer.
  • the structure of the mesomorphogenic group 4 will be such that this group will present a positive dielectric anisotropy in order to allow the orientation of the side chains of the polymer parallel to the electric field.
  • one or more permanent dipoles will be introduced into the architecture of the mesomorphogenic group. They will advantageously be chosen from the following: - NO 2 , - CN, F, CI, Br, - CFs or alkoxy.
  • the preparation of the mesomorphic polymeric material according to the invention does not pose any particular problem for those skilled in the art.
  • different solutions are possible for its synthesis. In some cases, it is better to first polymerize the skeleton and then attach the side chains to it. In other cases, it is advantageous to first synthesize the monomers 1 and 2 and then to carry out the copolymerization.
  • the other constituents (mesomorphogenic group 4, spacer 5 and 7, group 6 capable of generating the second harmonic) can be synthesized or linked in one or more times.
  • the mesomorphogenic group chosen is 4 hydroxy 4 'cyanobiphenyl. If the backbone is polysiloxane, it will be polymerized beforehand and the spacer will have a double bond at the end of the chain allowing the hydrosilylation reaction to take place. In the other backbone cases where the copolymerization of the monomers takes place in the last place, the spacer will carry the alcohol function at the end of the chain, which allows the subsequent esterification by the chloride of an a-substituted acrylic acid or not.
  • mesomorphogenic group is 4 hydroxy 4 'cyanobiphenyl.
  • This group can be introduced twice.
  • the first part of the mesomorphogenic group is grafted onto the corresponding spacer.
  • This set is then attached to the already polymerized skeleton (in the case of polysiloxane) or to an element of the skeleton (in other cases).
  • the second part of the mesomorphogenic group is then attached to its first part.
  • the group capable of generating the second harmonic is formed once or twice depending on the case.
  • FIG. 4 represents the chemical structure of a mesomorphic polymeric material according to the invention.
  • Parameter 0.424 designates the molar titer of azo monomer active in generation of second harmonic.
  • Its skeleton 3 is a polyacrylate.
  • the group 6 capable of generating the second harmonic is described in more detail in FIG. 5.
  • the abscissa axis carries the temperature T in degrees centigrade. This diagram was noted during the rise in temperature of a 4.27 mg mass sample and for a heating rate of 10 ° C / min.
  • the texture of this copolymer, observed by optical microscopy between the crossed analyzer and polarizer, is characteristic of a nematic mesophase.
  • this copolymer was melted on a glass slide 10 covered with a system of interdigitated electrodes 11 and 12 of the type shown in FIG. 8. These electrodes are transparent and for example made of mixed oxide tin and indium. The spacing between two consecutive fingers is around 80 ⁇ m.
  • the glass slide 10 covered with the copolymer is left for around ten minutes at 150 ° C. on a bench of the Kofler type in order to allow the degassing of the polymer, then a second glass slide 15 is deposited on the molten polymer.
  • FIG. 7 represents the cell used to obtain an oriented film. We find there, but seen in profile, the glass slide 10 supporting the electrodes 11 and 12.
  • Two shims 13 and 14, for example in a material such as "Mylar @" keep the strips 10 and 15 at a spacing of 130 ⁇ m.
  • the polymer 16 is therefore confined in the space defined by the blades and the shims.
  • the cell is then cooled to room temperature and then sealed with an "araldite” type adhesive.
  • the orientation of the side chains of the polymer is obtained by applying a DC voltage of around 160 V across the electrodes 11 and 12, the cell being brought to a temperature of around 120 ° C and then cooled to ambient temperature while maintaining the voltage across the electrodes.
  • the cell If the oriented film is irradiated in the vitreous state by means of a laser beam of wavelength 1.06 ⁇ m, the cell generates an electromagnetic wave of length 0.53 ⁇ m.
  • the non-linear response coefficient obtained is 0.12 ⁇ 10 -6 ues, which corresponds to an intensity efficiency approximately 300 times greater than that of lithium niobiate.
  • This example clearly demonstrates the superiority of the material according to the invention compared to the polymeric material mentioned above and whose non-linear response coefficient is 6.10-9 ues.
  • copolymers according to the invention can find applications in numerous fields of optoelectronics such as optical communications and integrated optics. In the latter field, polymers are of specific interest since they can be deposited on substrates of natures, therefore with different refractive indices.

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  • Physics & Mathematics (AREA)
  • Chemical & Material Sciences (AREA)
  • Nonlinear Science (AREA)
  • Optics & Photonics (AREA)
  • Organic Chemistry (AREA)
  • General Physics & Mathematics (AREA)
  • Materials Engineering (AREA)
  • Engineering & Computer Science (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)
  • Silicon Polymers (AREA)

Claims (7)

1. Mesomorpher Polymerstoff, dessen Struktur ein Skelett aufweist, an das Seitenketten angebunden sind, wobei der Stoff aus der Vereinigung zweier Monomere hervorgeht, die je eine Komponente des Skeletts sowie eine für dieses Monomer charakteristische Seitenkette besitzen, dadurch gekennzeichnet, daß
- das Skelett (3) ein Polyacrylat, ein Polymethacrylat, ein Polychloracrylat oder ein Polysiloxan ist;
- die Seitenkette aus einem für die Monomere (1, 2) spezifischen Element und aus einer Abstandskomponente (5, 7) besteht, die deren Anbindung an das Skelettelement ermöglicht;
- die Abstandskomponente von Typ -(CHz)n- mit 2≤n≤15, oder (CH2-CH2-0)n- mit 1≤n≤5 ist;
- das für das erste Monomer (1) spezifische Element eine mesomorphogene Gruppe (4) ist, welche eine positive dielektrische Anisotropie besitzt;
- das für das zweite Monomer spezifische Element eine Gruppe (6) mit folgender Struktur ist:
D - (System mit dilokalisierten Pi-Elektronen) - A,
wobei D eine Elektronendonatorgruppierung und A eine Elektronenakzeptorgruppierung ist und dieses spezifische Element mit dem Abstandshalter auf der Seite der D-Gruppierung verbunden ist.
2. Polymerstoff nach Anspruch 1, dadurch gekennzeichnet, daß die mesomorphogene Gruppe (4) mindestens einen Dipol vom Typ -N02, -CN, F, Cl, Br, -CF3 oder einen Alkoxydipol aufweist.
3. Polymerstoff nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß die D-Gruppierung eine der folgenden chemischen Funktionen ist: sekundäre Amine -NHR-, tertiäre Amine - NR1R2, ein in eine Ätherverbindung mit dem System delokalisierter Pi-Elektronen einbezogenes Sauerstoffatom oder ein in eine Thioätherverbindung mit dem System delokalisierter Elektronen einbezogenes Schwefelatom, wobei die Radikale R, Ri und R2 Alkyle sind.
4. Polymerstoff nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß die A-Gruppierung eine der folgenden chemischen Funktionen ist: -N02, -NO, -CN,
Figure imgb0021
wobei das Radikal R3 ein Alkyl ist.
5. Polymerstoff nach einem beliebigen der Ansprüche 1 bis 4, dadurch gekennzeichnet, daß das System delokalisierter Pi-Elektronen eines der folgenden Systeme ist:
-(CH = CH)n-, mit i≤n≤5
Figure imgb0022
, mit 1≤n≤3
Figure imgb0023
Figure imgb0024
, mit 1≤n≤3
Figure imgb0025
6. Polymerstoff nach Anspruch 5, dadurch gekennzeichnet, daß das Skelett (3) eine Polyacrylat, die Abstandskomponente (5, 7) die Gruppe - (CH2)6 - und die mesomorphogene Gruppe (4) die Gruppe
Figure imgb0026
ist, wobei die D-Gruppierung ein Sauerstoffatom, die A-Gruppierung eine Cyanofunktion und das System delokalisierter Pi-Elektronen das folgende System ist:
Figure imgb0027
7. Polymerstoff nach Anspruch 6, dadurch gekennzeichnet, daß die molaren Anteile des ersten und des zweiten Monomers im Kopolymer 0,576 bzw. 0,424 betragen.
EP87400816A 1986-04-15 1987-04-10 Mesomorpher Polymerwirkstoff, verwendungsfähig zur Nichtlinearoptik Expired - Lifetime EP0244288B1 (de)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR8605362 1986-04-15
FR8605362A FR2597109B1 (fr) 1986-04-15 1986-04-15 Materiau polymerique mesomorphe utilisable en optique non lineaire

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EP0244288A1 EP0244288A1 (de) 1987-11-04
EP0244288B1 true EP0244288B1 (de) 1990-05-23

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US (1) US4894263A (de)
EP (1) EP0244288B1 (de)
JP (1) JPS62243604A (de)
DE (1) DE3762867D1 (de)
FR (1) FR2597109B1 (de)

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Publication number Publication date
EP0244288A1 (de) 1987-11-04
US4894263A (en) 1990-01-16
DE3762867D1 (de) 1990-06-28
JPS62243604A (ja) 1987-10-24
FR2597109B1 (fr) 1988-06-17
FR2597109A1 (fr) 1987-10-16

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